Chloro­bis­[N-ethoxy­carbonyl-N′-(p-methoxy­phenyl)­thio­urea-κS]copper(I)

The title copper(I) complex, [CuCl(C₁₁H₁₄N₂O₃S)₂], was synthesized by the redox reaction of cupric chloride with the corresponding thio­urea derivative as reducing agent. The Cu^I coordination environment is trigonal planar, involving two S atoms and one Cl atom. The presence of intramolecular hydrogen bonds leads to the formation of a cis conformation and promotes the stability of the complex.

S1. Comment

Complexes of thiourea derivatives have been reported in several papers (Guillon et al., 1996, 1998), and these compounds have been popularly used in organic synthesis, such as in the metal-catalyzed asymmetric reduction of carbonyl compounds and carbonylative cyclization of o-hydroxylarylacetylenes (Touchard et al., 1997; Nan et al., 2000). Of all the thiourea derivatives, the N-substituted-N'-acylthiourea compounds have received the most attention, because the existence of acyl and thiocarbonyl groups in these complexes enhances the coordination ability of the ligands, which readily form supramolecular structures via hydrogen bonds. In our previous work (Zhang et al., 2003a, 2003b), a series of complexes with thiourea derivatives were synthesized and characterized, and the coordination behavior of thiourea derivatives was discussed. The preparation of the title complex, (I), and its crystal structure are reported here.

In many cases of synthesis of copper complexes, irreversible Cu^II/Cu^I systems have been observed (Guillon et al., 1996, 1998), and there are many reports of the reduction of Cu^II in the presence of thione derivatives (Jeannin et al., 1979; Raper, 1985; Karagiannidis et al., 1990). For the synthesis of complex (I), the cuprous complex was obtained by the redox reaction of cupric ions with the thiourea ligand. The reducing agent in this reaction is the thiourea ligand, N-(p-methoxyphenyl)-N'-(ethoxycarbonyl)thiourea, according to previous publications (Jeannin et al. 1979). This reaction is similar to those reported by Shen et al. (1997) and Zhang et al. (2003b).

In the molecular structure of (I), the two acylthiourea molecules adopt a cis conformation relative to the central Cu^I ion (Fig. 1) because of the existence of intramolecular hydrogen bonds between the Cl⁻ atom and H atoms bonded to atoms N2 and N4 (Table 2). The Cu^I ion in complex (I) has trigonal geometry, composed of two S atoms from two thiourea ligands and one Cl⁻ ion (Table 1). These atoms lie on a least-squares plane, the mean deviation from the plane being 0.0034 Å.

The existence of intramolecular hydrogen bonds in carbonylthiourea evidently influences its coordination properties and promotes the stability of the complex it forms. In cis-bis(N-Benzoyl-N'-propylthiourea)dichloroplatinum(II) (Bourne & Koch, 1993), the two ligand molecules bind to the Pt^II ion via the S atoms only, the carbonyl O atoms being locked into position by hydrogen bonds similar to those in the free ligand. The same observation was reported for a Cu^I complex by Shen et al. (1997) and Zhang et al. (2003b). By comparison, in N,N-disubstituted carbonylthiourea complexes, the carbonyl O atom commonly participates in coordination with the central metal ion, for example in the Pt^II and Cu^II complexes (Koch et al., 1994; Richter et al., 1980). This behavior is due to the absence of a thioamide H atom in the N,N-disubstituted carbonylthiourea, which means that no hydrogen bonds can form. This hypothesis is confirmed in complex (I), in which there are four intramolecular hydrogen bonds in the molecule (Table 2). Acyl atoms O2 and O5 form hydrogen bonds with the H atoms on atoms N1 and N3. Since they are locked into a planar six-membered ring formed by these hydrogen bonds, the acyl O atoms in the ligands cannot take part in the coordination with the Cu^I ion in the same way as the S atoms.

S2. Experimental

The N-(p-methoxyphenyl)-N'-(ethoxycarbonyl)thiourea ligand was synthesized according to the method reported by Zhang et al. (2003b). To an ethanol (30 ml) solution of the ligand (2 mmol) was added an ethanol solution (volume?) of cupric chloride (1 mmol). After stirring the solution at room temperature for 2 h, the mixture was filtered to obtain a white solid, which was then dried in air (yield 34%). Single crystals of (I) were obtained, after one week, by slow evaporation of a chloroform solution. Analysis calculated for C₂₂H₂₈ClCuN₄O₆S₂: C 43.45, H 4.61, N 9.22%; found: C 43.00, H 4.05, N 8.89%. IR (KBr disc): 3115 (versus), 1724 (versus), 1558 (s), 1530 (s), 1513 (versus), 1253 (versus), 1186 (s), 1040 (s), 834 (w), 769 (w), 684 (w), 521 (w). 1H NMR (Benzene-d₆): 0.92 (3H, CH3), 3.19 (3H, ArOCH3), 5.00 (2H, CH2), 7.16 (4H, Ar—H), 11.46 (1H, NH), 11.88 (1H, NH).

S3. Refinement

H atoms bonded to N atoms were found by difference Fourier methods and refined isotropically. H atoms bonded to C atoms were included in calculated positions (C—H = 0.93–0.97 Å) using a riding model.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXT (Bruker, 1998)L; software used to prepare material for publication: SHELXTL.

Figures

Figure 1 View of the title compound showing the atomic labeling. Displacement ellipsoids are drawn at the 50% probability level. Intramolecular hydrogen bonds are indicated by dashed lines.

Chlorobis[N-(ethoxycarbonyl)-N'-(p-methoxyphenyl)thiourea-κS]copper(I)

Crystal data

[CuCl(C11H14N2O3S)2]	Dx = 1.453 Mg m^−3
Mr = 607.59	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 949 reflections
a = 13.648 (3) Å	θ = 2.5–23.4°
b = 13.254 (3) Å	µ = 1.08 mm^−1
c = 15.358 (6) Å	T = 293 K
V = 2778.1 (13) Å^3	Block, colorless
Z = 4	0.26 × 0.24 × 0.18 mm
F(000) = 1256

Data collection

Bruker SMART CCD area-detector diffractometer	5690 independent reflections
Radiation source: fine-focus sealed tube	3568 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ and ω scans	θmax = 26.6°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −17→16
Tmin = 0.654, Tmax = 0.824	k = −16→10
15513 measured reflections	l = −19→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0408P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5690 reflections	Δρmax = 0.29 e Å^−3
342 parameters	Δρmin = −0.47 e Å^−3
5 restraints	Absolute structure: Flack (1983), 2678 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.438 (16)

Special details

Experimental. The infrared spectrum was recorded on a Nicolet NEXUS 670 F T—IR spectrophotometer using KBr discs. 1H NMR spectra were recorded on an Advance 300 Bruker spectrometer with Benzene-d6 as solvent.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.13153 (3)	0.13893 (3)	0.04286 (6)	0.05104 (15)
Cl1	0.12961 (8)	0.30854 (6)	0.04538 (18)	0.0680 (3)
S1	0.25076 (8)	0.05389 (8)	0.10676 (9)	0.0509 (3)
S2	0.01256 (8)	0.05482 (8)	−0.02238 (9)	0.0583 (4)
O1	0.5380 (2)	−0.2942 (3)	0.2340 (2)	0.0639 (10)
O2	0.4578 (2)	0.2951 (3)	0.2146 (3)	0.0674 (10)
O3	0.3396 (3)	0.3981 (3)	0.1651 (3)	0.0615 (11)
O4	−0.2819 (2)	−0.2938 (3)	−0.1406 (3)	0.0654 (11)
O5	−0.2006 (2)	0.2941 (3)	−0.1222 (3)	0.0640 (10)
O6	−0.0826 (3)	0.3974 (3)	−0.0729 (3)	0.0568 (10)
N1	0.4173 (3)	0.1013 (3)	0.1835 (3)	0.0537 (11)
H1	0.460 (3)	0.146 (3)	0.201 (3)	0.064*
N2	0.3204 (3)	0.2353 (3)	0.1454 (4)	0.0483 (12)
H2	0.269 (2)	0.253 (3)	0.116 (3)	0.058*
N3	−0.1602 (3)	0.1002 (4)	−0.0869 (3)	0.0554 (12)
H3	−0.205 (3)	0.145 (3)	−0.098 (3)	0.067*
N4	−0.0631 (3)	0.2356 (3)	−0.0516 (3)	0.0465 (11)
H4	−0.0071 (19)	0.255 (3)	−0.030 (3)	0.056*
C1	0.6196 (4)	−0.3328 (6)	0.1880 (5)	0.088 (2)
H1A	0.6057	−0.3327	0.1267	0.132*
H1B	0.6326	−0.4005	0.2068	0.132*
H1C	0.6759	−0.2913	0.1992	0.132*
C2	0.5097 (3)	−0.1970 (4)	0.2168 (4)	0.0494 (14)
C3	0.4284 (3)	−0.1624 (4)	0.2605 (3)	0.0549 (13)
H3A	0.3949	−0.2053	0.2980	0.066*
C4	0.3966 (3)	−0.0664 (4)	0.2494 (3)	0.0551 (12)
H4A	0.3418	−0.0438	0.2795	0.066*
C5	0.4456 (3)	−0.0019 (4)	0.1935 (3)	0.0456 (12)
C6	0.5263 (4)	−0.0353 (4)	0.1507 (3)	0.0588 (13)
H6	0.5600	0.0082	0.1138	0.071*
C7	0.5589 (3)	−0.1333 (4)	0.1612 (4)	0.0593 (14)
H7	0.6137	−0.1559	0.1309	0.071*
C8	0.3356 (4)	0.1332 (4)	0.1487 (3)	0.0439 (12)
C9	0.3818 (4)	0.3096 (4)	0.1793 (3)	0.0550 (12)
C10	0.3926 (4)	0.4870 (4)	0.1952 (4)	0.0729 (16)
H10A	0.4041	0.4829	0.2574	0.087*
H10B	0.4553	0.4921	0.1659	0.087*
C11	0.3320 (5)	0.5746 (4)	0.1750 (6)	0.118 (3)
H11A	0.3241	0.5798	0.1131	0.177*
H11B	0.3632	0.6344	0.1967	0.177*
H11C	0.2690	0.5670	0.2020	0.177*
C12	−0.3559 (5)	−0.3367 (6)	−0.0884 (5)	0.094 (2)
H12A	−0.3371	−0.3326	−0.0283	0.141*
H12B	−0.3648	−0.4061	−0.1043	0.141*
H12C	−0.4161	−0.3006	−0.0971	0.141*
C13	−0.2540 (3)	−0.1967 (4)	−0.1233 (4)	0.0469 (13)
C14	−0.3016 (3)	−0.1339 (4)	−0.0655 (4)	0.0593 (13)
H14	−0.3562	−0.1572	−0.0352	0.071*
C15	−0.2687 (3)	−0.0367 (4)	−0.0523 (3)	0.0563 (13)
H15	−0.3003	0.0052	−0.0126	0.068*
C16	−0.1893 (3)	−0.0023 (4)	−0.0979 (3)	0.0445 (12)
C17	−0.1411 (3)	−0.0645 (3)	−0.1552 (3)	0.0480 (11)
H17	−0.0865	−0.0412	−0.1852	0.058*
C18	−0.1741 (3)	−0.1620 (3)	−0.1682 (3)	0.0509 (12)
H18	−0.1420	−0.2041	−0.2074	0.061*
C19	−0.0764 (3)	0.1341 (4)	−0.0563 (3)	0.0455 (12)
C20	−0.1239 (3)	0.3094 (4)	−0.0861 (3)	0.0486 (12)
C21	−0.1336 (4)	0.4854 (4)	−0.1089 (4)	0.0656 (14)
H21A	−0.1992	0.4901	−0.0850	0.079*
H21B	−0.1384	0.4799	−0.1717	0.079*
C22	−0.0756 (5)	0.5749 (4)	−0.0846 (5)	0.091 (2)
H22A	−0.0795	0.5852	−0.0229	0.137*
H22B	−0.1011	0.6331	−0.1142	0.137*
H22C	−0.0085	0.5649	−0.1011	0.137*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0421 (3)	0.0469 (2)	0.0641 (3)	0.0012 (3)	−0.0088 (3)	−0.0012 (5)
Cl1	0.0542 (6)	0.0410 (5)	0.1089 (9)	0.0010 (5)	−0.0220 (7)	−0.0001 (14)
S1	0.0452 (6)	0.0429 (6)	0.0645 (8)	−0.0017 (5)	−0.0121 (6)	0.0003 (6)
S2	0.0469 (7)	0.0412 (6)	0.0867 (10)	0.0069 (5)	−0.0218 (7)	−0.0072 (7)
O1	0.066 (2)	0.054 (3)	0.071 (3)	0.0085 (18)	0.009 (2)	0.009 (2)
O2	0.049 (2)	0.061 (3)	0.092 (3)	−0.0015 (18)	−0.022 (2)	−0.010 (2)
O3	0.056 (2)	0.041 (3)	0.087 (3)	−0.007 (2)	−0.020 (2)	−0.002 (2)
O4	0.073 (2)	0.054 (3)	0.069 (3)	−0.016 (2)	0.002 (2)	−0.002 (2)
O5	0.045 (2)	0.056 (2)	0.091 (3)	0.0059 (17)	−0.019 (2)	0.017 (2)
O6	0.052 (2)	0.041 (2)	0.077 (3)	0.0091 (18)	−0.003 (2)	0.0073 (19)
N1	0.041 (3)	0.048 (3)	0.072 (3)	0.001 (2)	−0.015 (2)	−0.004 (2)
N2	0.040 (2)	0.045 (3)	0.060 (3)	−0.004 (2)	−0.011 (2)	−0.003 (2)
N3	0.041 (3)	0.047 (3)	0.079 (4)	0.009 (2)	−0.013 (2)	0.004 (2)
N4	0.043 (2)	0.037 (2)	0.060 (3)	0.0061 (19)	−0.013 (2)	0.000 (2)
C1	0.101 (5)	0.073 (5)	0.090 (5)	0.034 (4)	0.027 (4)	0.011 (4)
C2	0.044 (3)	0.053 (4)	0.051 (3)	0.001 (2)	−0.006 (3)	0.002 (3)
C3	0.050 (3)	0.058 (3)	0.057 (3)	0.000 (2)	0.006 (2)	0.011 (2)
C4	0.041 (3)	0.067 (3)	0.057 (3)	0.006 (3)	0.008 (2)	−0.001 (3)
C5	0.034 (3)	0.050 (3)	0.053 (3)	0.006 (2)	−0.003 (2)	−0.003 (2)
C6	0.058 (3)	0.055 (3)	0.064 (3)	−0.006 (3)	0.006 (3)	0.014 (2)
C7	0.047 (3)	0.066 (4)	0.065 (4)	0.010 (3)	0.013 (3)	0.006 (3)
C8	0.036 (2)	0.049 (3)	0.047 (3)	−0.001 (2)	0.003 (2)	−0.001 (3)
C9	0.049 (3)	0.059 (3)	0.057 (3)	−0.004 (3)	0.000 (3)	−0.004 (3)
C10	0.067 (4)	0.057 (3)	0.094 (4)	−0.021 (3)	−0.018 (3)	−0.009 (3)
C11	0.084 (4)	0.059 (4)	0.211 (9)	0.002 (3)	−0.051 (5)	−0.034 (5)
C12	0.114 (5)	0.069 (5)	0.099 (6)	−0.047 (4)	0.017 (4)	0.010 (4)
C13	0.041 (3)	0.046 (3)	0.054 (3)	−0.004 (2)	−0.005 (2)	0.002 (3)
C14	0.051 (3)	0.061 (3)	0.066 (3)	−0.009 (3)	0.014 (3)	0.002 (3)
C15	0.046 (3)	0.064 (3)	0.059 (3)	−0.003 (2)	0.009 (2)	−0.007 (3)
C16	0.034 (3)	0.043 (3)	0.057 (3)	0.000 (2)	−0.009 (2)	0.005 (2)
C17	0.041 (3)	0.051 (3)	0.052 (3)	−0.002 (2)	0.003 (2)	0.008 (2)
C18	0.046 (3)	0.056 (3)	0.051 (3)	0.001 (2)	0.002 (2)	−0.002 (2)
C19	0.044 (3)	0.043 (3)	0.049 (3)	−0.001 (2)	−0.003 (2)	−0.006 (2)
C20	0.049 (3)	0.042 (3)	0.056 (3)	0.006 (3)	0.009 (3)	0.005 (2)
C21	0.069 (4)	0.051 (3)	0.076 (4)	0.011 (3)	0.001 (3)	0.015 (3)
C22	0.098 (5)	0.048 (3)	0.127 (6)	0.009 (3)	−0.017 (4)	0.016 (4)

Geometric parameters (Å, º)

Cu1—S1	2.2095 (13)	C3—H3A	0.9300
Cu1—S2	2.2098 (13)	C4—C5	1.385 (6)
Cu1—Cl1	2.2484 (10)	C4—H4A	0.9300
S1—C8	1.691 (5)	C5—C6	1.357 (6)
S2—C19	1.689 (5)	C6—C7	1.382 (6)
O1—C2	1.370 (6)	C6—H6	0.9300
O1—C1	1.415 (6)	C7—H7	0.9300
O2—C9	1.186 (5)	C10—C11	1.458 (8)
O3—C9	1.325 (7)	C10—H10A	0.9700
O3—C10	1.458 (6)	C10—H10B	0.9700
O4—C13	1.367 (6)	C11—H11A	0.9600
O4—C12	1.409 (6)	C11—H11B	0.9600
O5—C20	1.202 (5)	C11—H11C	0.9600
O6—C20	1.311 (6)	C12—H12A	0.9600
O6—C21	1.465 (6)	C12—H12B	0.9600
N1—C8	1.307 (6)	C12—H12C	0.9600
N1—C5	1.429 (6)	C13—C18	1.369 (6)
N1—H1	0.865 (10)	C13—C14	1.380 (7)
N2—C8	1.370 (6)	C14—C15	1.380 (6)
N2—C9	1.394 (7)	C14—H14	0.9300
N2—H2	0.864 (10)	C15—C16	1.369 (6)
N3—C19	1.315 (7)	C15—H15	0.9300
N3—C16	1.425 (7)	C16—C17	1.375 (7)
N3—H3	0.870 (10)	C17—C18	1.383 (6)
N4—C19	1.359 (6)	C17—H17	0.9300
N4—C20	1.387 (6)	C18—H18	0.9300
N4—H4	0.870 (10)	C21—C22	1.474 (7)
C1—H1A	0.9600	C21—H21A	0.9700
C1—H1B	0.9600	C21—H21B	0.9700
C1—H1C	0.9600	C22—H22A	0.9600
C2—C3	1.376 (6)	C22—H22B	0.9600
C2—C7	1.377 (7)	C22—H22C	0.9600
C3—C4	1.354 (6)
S1—Cu1—S2	119.03 (4)	O3—C10—H10A	110.3
S1—Cu1—Cl1	120.72 (5)	C11—C10—H10B	110.3
S2—Cu1—Cl1	120.24 (5)	O3—C10—H10B	110.3
C8—S1—Cu1	110.89 (18)	H10A—C10—H10B	108.5
C19—S2—Cu1	110.77 (17)	C10—C11—H11A	109.5
C2—O1—C1	117.7 (4)	C10—C11—H11B	109.5
C9—O3—C10	116.6 (4)	H11A—C11—H11B	109.5
C13—O4—C12	118.0 (4)	C10—C11—H11C	109.5
C20—O6—C21	116.5 (4)	H11A—C11—H11C	109.5
C8—N1—C5	125.7 (4)	H11B—C11—H11C	109.5
C8—N1—H1	119 (3)	O4—C12—H12A	109.5
C5—N1—H1	116 (3)	O4—C12—H12B	109.5
C8—N2—C9	126.3 (4)	H12A—C12—H12B	109.5
C8—N2—H2	114 (3)	O4—C12—H12C	109.5
C9—N2—H2	119 (3)	H12A—C12—H12C	109.5
C19—N3—C16	127.6 (4)	H12B—C12—H12C	109.5
C19—N3—H3	117 (3)	O4—C13—C18	116.1 (4)
C16—N3—H3	115 (3)	O4—C13—C14	124.1 (4)
C19—N4—C20	126.7 (4)	C18—C13—C14	119.8 (4)
C19—N4—H4	115 (3)	C15—C14—C13	120.3 (4)
C20—N4—H4	118 (3)	C15—C14—H14	119.8
O1—C1—H1A	109.5	C13—C14—H14	119.8
O1—C1—H1B	109.5	C16—C15—C14	119.6 (5)
H1A—C1—H1B	109.5	C16—C15—H15	120.2
O1—C1—H1C	109.5	C14—C15—H15	120.2
H1A—C1—H1C	109.5	C15—C16—C17	120.4 (5)
H1B—C1—H1C	109.5	C15—C16—N3	118.5 (5)
O1—C2—C3	116.5 (4)	C17—C16—N3	121.0 (4)
O1—C2—C7	124.0 (4)	C16—C17—C18	119.8 (4)
C3—C2—C7	119.5 (5)	C16—C17—H17	120.1
C4—C3—C2	120.7 (5)	C18—C17—H17	120.1
C4—C3—H3A	119.7	C13—C18—C17	120.0 (4)
C2—C3—H3A	119.7	C13—C18—H18	120.0
C3—C4—C5	120.3 (4)	C17—C18—H18	120.0
C3—C4—H4A	119.9	N3—C19—N4	118.2 (4)
C5—C4—H4A	119.9	N3—C19—S2	121.5 (4)
C6—C5—C4	119.3 (4)	N4—C19—S2	120.2 (3)
C6—C5—N1	118.7 (4)	O5—C20—O6	126.5 (5)
C4—C5—N1	121.9 (4)	O5—C20—N4	125.3 (5)
C5—C6—C7	120.8 (5)	O6—C20—N4	108.2 (4)
C5—C6—H6	119.6	O6—C21—C22	106.9 (4)
C7—C6—H6	119.6	O6—C21—H21A	110.3
C2—C7—C6	119.4 (4)	C22—C21—H21A	110.3
C2—C7—H7	120.3	O6—C21—H21B	110.3
C6—C7—H7	120.3	C22—C21—H21B	110.3
N1—C8—N2	117.6 (5)	H21A—C21—H21B	108.6
N1—C8—S1	122.7 (4)	C21—C22—H22A	109.5
N2—C8—S1	119.7 (4)	C21—C22—H22B	109.5
O2—C9—O3	126.8 (5)	H22A—C22—H22B	109.5
O2—C9—N2	125.7 (5)	C21—C22—H22C	109.5
O3—C9—N2	107.6 (5)	H22A—C22—H22C	109.5
C11—C10—O3	107.1 (4)	H22B—C22—H22C	109.5
C11—C10—H10A	110.3
S2—Cu1—S1—C8	177.77 (19)	C8—N2—C9—O3	−178.0 (5)
Cl1—Cu1—S1—C8	−3.0 (2)	C9—O3—C10—C11	−178.6 (6)
S1—Cu1—S2—C19	173.52 (19)	C12—O4—C13—C18	172.3 (5)
Cl1—Cu1—S2—C19	−5.7 (2)	C12—O4—C13—C14	−8.5 (8)
C1—O1—C2—C3	178.1 (5)	O4—C13—C14—C15	−179.6 (5)
C1—O1—C2—C7	−3.7 (7)	C18—C13—C14—C15	−0.5 (8)
O1—C2—C3—C4	178.1 (4)	C13—C14—C15—C16	1.0 (8)
C7—C2—C3—C4	−0.1 (8)	C14—C15—C16—C17	−1.3 (8)
C2—C3—C4—C5	0.3 (7)	C14—C15—C16—N3	176.4 (4)
C3—C4—C5—C6	−0.8 (7)	C19—N3—C16—C15	118.1 (6)
C3—C4—C5—N1	−176.7 (4)	C19—N3—C16—C17	−64.2 (7)
C8—N1—C5—C6	116.8 (6)	C15—C16—C17—C18	1.2 (7)
C8—N1—C5—C4	−67.3 (7)	N3—C16—C17—C18	−176.5 (4)
C4—C5—C6—C7	1.1 (8)	O4—C13—C18—C17	179.5 (4)
N1—C5—C6—C7	177.2 (5)	C14—C13—C18—C17	0.3 (7)
O1—C2—C7—C6	−177.7 (5)	C16—C17—C18—C13	−0.7 (7)
C3—C2—C7—C6	0.5 (8)	C16—N3—C19—N4	179.6 (5)
C5—C6—C7—C2	−1.0 (8)	C16—N3—C19—S2	−1.1 (8)
C5—N1—C8—N2	179.4 (5)	C20—N4—C19—N3	−8.9 (8)
C5—N1—C8—S1	−2.0 (8)	C20—N4—C19—S2	171.8 (4)
C9—N2—C8—N1	−3.3 (8)	Cu1—S2—C19—N3	−171.2 (4)
C9—N2—C8—S1	178.0 (4)	Cu1—S2—C19—N4	8.0 (5)
Cu1—S1—C8—N1	−174.2 (4)	C21—O6—C20—O5	−2.5 (8)
Cu1—S1—C8—N2	4.5 (5)	C21—O6—C20—N4	177.0 (4)
C10—O3—C9—O2	0.7 (8)	C19—N4—C20—O5	3.7 (9)
C10—O3—C9—N2	−179.6 (5)	C19—N4—C20—O6	−175.8 (5)
C8—N2—C9—O2	1.7 (9)	C20—O6—C21—C22	178.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.87 (4)	1.99 (4)	2.670 (6)	134 (4)
N2—H2···Cl1	0.87 (3)	2.31 (3)	3.175 (5)	176 (2)
N3—H3···O5	0.87 (4)	2.01 (4)	2.682 (6)	133 (4)
N4—H4···Cl1	0.87 (3)	2.31 (3)	3.174 (4)	172 (4)